Cu–BTC (also known as HKUST-1) is a well-characterized metal–organic framework material produced in an industrial scale and widely studied for a number of potential applications by the scientific community. The co-existence of Cu+ and Cu2+ entities has already been observed in this material, but the presence of Cu+ ions was attributed to oxide impurities. The results presented here clearly demonstrate that Cu+ ions can be present in high concentrations inside the hybrid structure. Furthermore, switching between the two copper oxidation states can be induced by redox treatments, using vacuum and/or reducing gases at different sample temperatures.